Flex-fuel hydrogen reformer for IC engines and gas turbines

ABSTRACT

An on-board Flex-Fuel H 2  reforming apparatus provides devices and the methods of operating these devices to produce a combustible reformate containing H 2  and CO from hydrocarbons and bio-fuels. For this generator, one or more parallel autothermal reformers are used to convert the fuels into the reformate over Pt group metal catalysts, and the produced reformate is then cooled, compressed and stored in vessels at a pressure between 1 to 100 atmospheres. The reformate from the storage vessels is used either as the sole fuel or is mixed with other fuels as the fuel mixture for a lean burn engine/gas turbine. For this system, the pressure of the storage vessels and the flow control curves are used directly to control the amount of the reformers&#39; reformate flow output.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Patent Application No. 61/688,853 filed May 23, 2012 andpriority under 35 U.S.C. § 120 to U.S. patent application Ser. No.13/900,479 filed May 22, 2013. The foregoing applications areincorporated by reference herein.

BACKGROUND OF THE INVENTION

Internal Combustion Engines and Gas Turbines

In the 20th century, various types of internal combustion (IC) enginesand gas turbines have successfully been developed, and have been widelyused over the years in the stationary power generation, transportationand utility applications. For example, the 2-stroke and 4-strokegasoline engines are used for motorcycle, chainsaw, lawn mower, weedeater, automobile, small power generator etc, the diesel engines areused for truck, bus, stationary power generator etc, and the gasturbines are used for airplanes, power generators etc. Currently, mostof the IC engines and gas turbines utilize homogeneous flame combustionof various hydrocarbons (HC) to generate power, and it is known that theignition timing, the composition of the fuel/air mixture, thevaporization of the fuels, and the temperature and pressure at themoment of ignition are very important for a complete combustion.However, despite all the necessary controls and the technology advancesover the years, any internal combustion engine or gas turbine will stillemit pollutants such as unburned hydrocarbons, CO, NO_(x), dieselparticulates etc.

Currently, to reduce the HC, CO, NO_(x) and diesel particulatepollutants from the IC engine's exhaust gas, catalytic converters,NO_(x) traps and/or diesel particulate traps, which contains supportedmonolithic Pt group metal catalysts, have successfully been usedcommercially for several decades. For this pollution removingtechnology, an on-board microprocessor/computer (i.e. Emission ControlUnit—ECU) as well as various electronic and mechanical devices/sensorsare used to reduce the pollutants by controlling the air/fuel ratio andthe ignition timing of the combustion gas.

Various other types of IC engines have also been developed successfullyin recent years, and these engines can use different fuels such ashydrogen, natural gas, liquefied propane gas (LPG), gasoline/ethanolmixture (gasohol), diesel/bio-diesel mixture etc.

Hydrogen—Hydrocarbon Mixture as Engine Fuel:

To reduce the automobile's pollution, U.S. Pat. Nos. 3,955,941,3,971,847, 3,982,910, 4,033,133, herein incorporated by reference, hadinvented several on-board reformers in the 1970s for producing H₂ fromgasoline. The produced reformate was then mixed with additional amountof gasoline and air to form a very lean fuel mixture, and this mixturewas then injected into an engine to perform lean combustion inside thecombustion chambers. However, by using either homogeneous partialoxidation reactions or by using very low activity catalysts to produceH₂ from gasoline, these on-board reformers were bulky and also could notavoid coke formation in the reaction zones.

To improve engine's thermal efficiency and reduce automobile'spollution, several other patents and technical reports/publications hadalso attempted to produce H₂ from fuels by various catalytic processes.For example, U.S. Pat. Nos. 5,947,063, 3,915,125 and 4,109,461, hereinincorporated by reference, described various on-board reformers toproduce H₂ and CO gas from gasoline by catalytic partial oxidationreactions. U.S. Pat. No. 4,567,857, herein incorporated by reference,described a reformer to produce H₂ and CO catalytically by methanolsteam reforming reaction. However, these pre-engine hydrogen reformershave not successfully been developed as commercial products, probablydue to coking formation inside the bulky reformer. Instead, varioustypes of catalytic converters, which are installed in the exhaust pipeafter the engine, have commercially been used successfully to reduce theautomobile's pollution since 1975.

Hydrogen can also be produced by another non-catalytic process. In U.S.Pat. Nos. 5,425,332, 7,028,644 and 7,225,787, herein incorporated byreference, an on-board Plasmatron fuel processor can generateelectrically conducting gas (plasma), which can initiate non-catalyticpartial oxidation reactions of various HC and bio-fuels to producehydrogen for an IC engines. By mixing this reformate gas with theengine's inlet air stream, the engine can be operated in the ultra leanmode at a higher compression ratio (D. R. Cohn, Fusion Power Assoc.Meeting, Nov. 21, 2003). Thus, it was reported that this on-boardPlasmatron fuel process can increase engine's efficiency by 20-25%,reduce NOx emission up to 90% and decrease diesel engine's exhaustemission by 90% (Diamond and Cohn, Office of TransportationTechnologies, press release December 2001).

U.S. Pat. No. 7,721,682, herein incorporated by reference, describes asystem and a method for producing, dispensing, using and monitoring a H₂enriched natural gas (i.e. “Hythane”) as engine fuels. This pre-mixedhigh pressure Hythane gas, which is available from a storage vessel atsome local vehicle refueling stations, has recently been used to reduceNO_(x) emission and to improve engine's combustion efficiency of dieseltrucks.

In the last several decades, new technologies, which can producehydrogen from HC/bio-fuels over the advanced Pt group metal catalystsunder very high space velocity conditions, have successfully beendeveloped for several different types of fuel cell applications.Therefore, a specifically designed economic and compact on-boardhydrogen reforming apparatus, which utilizes these new advancedcatalysts and new hydrogen production technologies with the powerfulmicroprocessor controllers, sensors and other special devices, caneffectively improve the patented on-board hydrogen reformers and thesteady state fuel cell H₂ reformers as described previously. In otherwords, a new improved on-board hydrogen reforming apparatus, which isequipped with new devices and the new control strategy designedspecifically for the engine's transient operation mode, can have longreformer life without coke formation, and can successfully producehydrogen from hydrocarbons and/or bio-fuels efficiently and effectivelyfor IC engines/gas turbines.

The Brown Gas (HHO or H₂/O₂ Gas):

In recent years, the Brown gas (or so called HHO gas,www.hydrogen-boost.com, www.hydrogen-generators-usa.com, US 2012/0067304A1), which is the H₂ and O₂ gas mixture generated by the electrolysis ofdistilled water, has been added to the air/fuel mixture of a gasoline ora diesel truck engine as a supplemental fuel. With the help of somespecially designed IC chips, sensors and flow controllers, the air/fuelratio of the engine's inlet fuel mixture can be adjusted away from thestoichiometric condition and allow the IC engine to be operated in thelean combustion mode. By doing so, it is claimed that the engine's fuelmileage can be improved by 15-20% and can reduce the pollutions.

However, the corrosive nature of the KOH or NaOH electrolyte canpotentially cause permanent damage to the engines. Therefore, in orderto have a long term trouble free operation, the level and theconcentration of the electrolyte, the electrolyte's operatingtemperature and the safe operation of this combustible and potentiallyexplosive Brown Gas must constantly be monitored and maintained.

Catalytic EGR Oxidizer for IC Engines and Gas Turbines:

For the purpose of assisting and improving the combustion efficiency ofan IC engine and/or a gas turbine, U.S. Pat. No. 8,061,120, hereinincorporated by reference, describes a process of generating H₂/CO gasfrom various HC fuels and bio-fuels by an on-board EGR Oxidizer, whichis a catalytic autothermal (ATR) reformer. The primary purpose of thispatent is to use a catalytic reformer to replace the non-catalyticPlasmatron reformer for the mobile vehicle application.

According to this patent, a fuel mixture comprising hydrocarbons (HC)and/or bio-fuels, water/steam, air and portion of the engine's recycleexhaust gas is injected into an EGR Oxidizer. This fuel mixture issubsequently reacted over Pt group metal catalysts (pgm) inside the EGROxidizer's first reaction zone to produce a high pressure reformatecontaining steam, H₂, CO, CO₂, N₂, O₂ and unconverted HC. To improvecatalyst's durability and life without coke formation, the O₂/C, H₂O/Cand CO₂/C ratios of the inlet feed stream must be controlledindividually and/or simultaneously within a specific range (or limits)at a given reaction temperature and pressure, and also to keep the ATRreaction zone's temperature continuously between 150 and 1200° C. Thereformate so produced is then combined with additional amount of fuelsand fresh air to form a lean fuel mixture, and all fuels and combustiblecompounds in this mixture will be completely converted into CO₂ andsteam by a downstream engine/gas turbine.

A combination of an EGR Oxidizer and an IC engine/gas turbine can beused by itself as a driving device, or they can be combined with anelectric generator and a battery bank to produce and store electricityas a distributed mobile or a small stationary power generator.

For diesel and lean burn engines, the EGR Oxidizer can also be used toprovide reducing gases to regenerate the catalysts used in the NO_(x) ordiesel particulate filter traps. After regeneration, the traps cancontinuously be used to reduce emissions from an IC engine, dieseltruck, gas turbine, power plant etc

Electronic Fuel Injection:

By precisely controlling the amount of fuel injected, the ignitiontimings, and the air/fuel ratio of the fuel mixture, electronic fuelinjection (EFI) has commercially been adopted for almost everyautomobile since 1990. With the EFI system, every automobile can improveits gasoline mileage and reduce the pollutants.

To improve further the engine's thermal efficiency, U.S. Pat. Nos.8,091,536 and 8,396,644, herein incorporated by reference, havedeveloped duel fuel injecting system for injecting both H₂ and HC intothe combustion chambers. Especially, U.S. Pat. No. 8,396,644 hasdescribed a system and the detailed control strategy for injecting thecalculated amount of H₂/reformate from a storage tank and/or from areformer into a truck engine as the second fuel. However, the details ofthe reformer's operations, such as the process, catalysts and thereaction temperature, for producing reformate from fuels were notreveled in this patent. Furthermore, since the reformer's operation asdiscussed in this patent is directly related to the engine's speed andtorque (paragraph #0186), there is a high tendency to form coke insidethe reformer during the transient unsteady state operation, especiallyif diesel oil is used as the reformer's fuel.

Regeneration of NO_(x) Trap and Diesel Particulate Filter:

For lean burn diesel engines, the NO_(x) trap and the particulate filterare used to removed the pollutants. But, when the trap materials and/orthe filter have reached their saturation level, they are required to beregenerated with a reducing gas so that they can be used continuously.To produce reducing gases, WO01/34950 and U.S. Pat. Nos. 5,441,401,5,586,433, 6,845,610 and 7,610,752, herein incorporated by reference,have developed various devices and methods for producing H2 and COcatalytically by reforming diesel oil over various types of catalysts.In addition, a non-catalytic Plasmatron fuel processor as discussedpreviously can also produce H₂ rich reformate by the plasma partialoxidation reactions (Bromberg et al., Diesel Engine Emission ReductionWorkshop, Newport, R.I., Aug. 24-28, 2003). However, these on-boardreformers have not been widely used commercially, probably due to cokeformation and/or their short useful life during the applications.

BRIEF SUMMARY OF THE INVENTION

U.S. Pat. No. 8,061,120 describes a process for producing H₂ and CO fromvarious fuels by an on-board Catalytic EGR Oxidizer for IC engines/gasturbines. Using the same ATR reforming process, this newly inventedon-board Flex-Fuel H₂ reforming apparatus provides several practicaldevices and new methods of operating these devices for generating H₂ andCO reformate from hydrocarbons (HC) and bio-fuels. The improved on-boardFlex-Fuel H₂ reforming apparatus can be self-started without using anyexternal heat and power sources, and the produced high pressurereformate is stored in several vessels. Then, this product gas from thestorage vessels can be used to improve combustion efficiency of an ICengine/gas turbine, to regenerate catalysts in the NO_(x)/dieselparticulate filter traps and to provide H₂ for other mobile or smallstationary applications.

This on-board Flex-Fuel H₂ reforming apparatus provides devices and themethods of operating these devices comprising: (a). Providing one ormore parallel autothermal (ATR) reformers for producing H₂ and CO fromhydrocarbons and/or bio-fuels over supported and/or unsupported Pt groupcatalysts; (b). Providing one automatic control system comprising acontrol computer and/or microprocessors, flow meters/controllers,valves, pumps, sensors and thermocouples; (c). Providing a stream of theATR reformer's inlet fuel mixture comprising at least one oxidant, atleast one fuel and at least one water/steam selected from the reactantsupply group consisting of liquid fuel loop, gas fuel loop, water supplyloop, air supply loop, water electrolyzer loop, exhaust gas recycle(EGR) loop, water recycle loop and reformate recycle loop; (d). Reactingsaid stream of the inlet fuel mixture over said catalysts inside the ATRreformer to produce a reformate containing H₂ and CO from said fuels,and simultaneously controlling said fuel mixture's O₂/C, H₂O/C and CO₂/Cratios within a given range so that the maximum ATR reaction temperatureis kept constantly below 1200°; (e). Providing one or morevessels/manifolds for storing the condensed water for the reformers andalso the produced dry reformate from the ATR reformers between 1 to 100atmospheres for the downstream IC engine/gas turbines and/or fuel celldevices; (f). Providing one or more flow control curves for regulatingeach reactant's flow rate, the dry reformate composition and the totalreformer's flow output by the pressure of the storage vessels, whereinthe control curves which are stored in the control computer and/or inthe microprocessors should provide precisely an inlet fuel mixture tothe reformers at the specified O₂/C, H₂O/C and CO₂/C ratios, and (g).Reacting the start-up reactants over the catalysts to start or re-startrapidly the ATR reformers without external heat and electricity, whereintwo or more start-up reactants are selected from the group consisting offuels, air, the engine/gas turbine's recycle exhaust gas, the H₂/O₂gases from the electrolyzer, and the recycle reformate.

Depending on the pressure of the reformate storage vessels and thecontrol curves, the automatic control system is capable of downloading agroup of flow requirements (i.e. a group of flow set points) to all flowcontrollers to regulate simultaneously each reactant's flow rate. Thus,it can provide a specified fuel mixture to the ATR reformers by blendingall the reactants together as a single fuel mixture stream. To avoidcoking, deactivating or even melting of the catalysts, the O₂/C, H₂O/Cand CO₂/C ratios of the inlet fuel mixture must be maintained constantlywithin the specified limits, so that the maximum reactor temperature ofeach ATR reformer can constantly be controlled below 1200° C.(preferably <1000° C.). In addition, while keeping at the same specifiedO₂/C, H₂O/C and CO₂/C ratios, the control system can instantly andprecisely download a new set of flow requirements to all flowcontrollers during the operation, and each flow controller willproportionally increase/decrease its flow rate. Thus, the ATR reformerscan quickly increase/decrease the total amount of reformate with thesame gas composition to keep the pressure of the storage vessels within1 to 100 atmosphere.

For mobile applications, the engine's H₂ demand can fluctuate widely dueto idling and full speed operating conditions. Since the total amount ofreformate generated by the reformers is automatically controlled by thepressure of the storage vessels and is not directly controlled by theengine's speed/load, the reformers can mostly be operated under steadystate conditions, and they can smoothly changed from one steady state tothe next condition without being directly influenced by the engine'sspeed/load. In other words, this new operating control strategy is tominimize and/or to avoid any momentary and frequently suddenfluctuations of the O₂/C and H₂O/C ratios in the reformer's inlet gascomposition, so that it can prevent coke formation inside the reformersand, thus, can extend the Flex-Fuel H₂ reforming apparatus's durabilityand service life.

For a pressurized ATR reactor system used in the mobile applicationswhere space is limited, it is advantageous to use multiple smalldiameter reformers to replace a single large diameter reformer, becausethe multiple small reactors for a high pressure system are cheaper tomake, easier to maintain/replace/repair, and their flexibility inoperation can satisfy the engine's reformate requirements withoutoperating the reformers under unsteady state and coke formationconditions. Furthermore, since the inlet fuel mixture under O2/C<0.5 ismostly combustible and potentially explosive, it is important to useproper fuel injectors and also to minimize the total amount of fuelmixture injected into a reformer, so that any damages caused by systemmalfunctions can safely be reduced. For these reasons, this on-boardFlex-Fuel H₂ reforming apparatus comprises one or more parallel ATRreformers in the system. However, since each ATR reformer in the systemcan independently be operated by the control system automatically, thefollowing discussion for a single reformer can apply equally well toeach ATR reformer in the system.

Every ATR reformer in the system contains three reaction zones—the firstautothermal (i.e. catalytic partial oxidation/steam reforming—CPO/SR)zone, the second steam reforming (SR) zone and the third water gas shift(WGS) zone. A stream of fuel mixture with proper gas composition isintroduced into the inlet of the ATR reformer's first reaction zone, andthe produced reformate containing H₂ and CO will exit from the outlet ofthe reformer's third reaction zone. For this Flex-Fuel H₂ reformingapparatus, the inlet fuel mixture to the ATR reformers comprises mainlyO₂, water and fuel, and this fuel mixture may or may not contain inertgases such as N₂ and CO₂. Briefly, the water source can come from awater tank or from a water recycle loop; The fuel source can be one ormore components selected from the group consisting of any gaseous/liquidhydrocarbons and/or bio-fuels; The O₂ source can be O₂ from air, O₂ froma water electrolyzer, O₂ from an engine/turbine's exhaust gas recycleloop, or O₂ from a mixture containing >10% oxygen by combining togetherat least two of the above three oxygen sources.

Each ATR reformer in the Flex-Fuel H₂ reforming apparatus system iscapable of performing the following steps: (1). Receiving a stream ofinlet fuel mixture consisting of water, one or more fuels and O₂containing gas with or without diluents in a given range of O₂/C, H₂O/Cand CO₂/C ratios into the reformer's first CPO/SR reaction zone; (2).Reacting said inlet fuel mixture over Pt group metal catalysts with aresidence time <300 milliseconds (calculated at STP) in the first CPO/SRreaction zone; (3). Reacting further the fuel and reformate mixture fromstep 1 over Pt group metal catalysts with a residence time <5 seconds inthe second SR reaction zone; (4). Producing rapidly in steps 2 and 3 areformate stream comprising of steam, H₂, CO, CO₂, N₂, O₂ andunconverted fuels at a given temperatures between 150-1200° C. and agiven pressure between 1 to 100 atmosphere, and (5). Feeding theproduced reformate stream from step 4 into the reformer's third reactionzone with a residence time <100 seconds and then converting portion ofthe feed water and CO into hydrogen with or without Pt group metalcatalyst at a temperatures between 50 to 500° C. After the reformers,the produced ATR reformate can be cooled by a heat exchanger, thecondensed water will then be stored in a water tank and the dry gas willbe compressed and stored in one or more storage vessels at a pressurebetween 1 to 100 atmospheres.

The stored/accumulated high pressure reformate in the storage vesselscan be used as followings: (1). Combine the reformate with additionalamount of fuels and fresh air to form a lean fuel mixture as engine/gasturbine's fuel source; (2). Provide H₂ to generate the oxidationreaction heat over the catalysts to start up the reformer quickly fromroom temperature; (3). Provide H₂ to reduce the supported Pt group metalcatalysts or to regenerate catalysts in the catalytic converters, NO_(x)traps, diesel particulate filters etc.; (4). Provide H₂ to a mobilevehicle/device equipped with a solid oxide or proton exchange membranefuel cell stack for generating electricity, and (5). Provide reformateto a small diesel engine and/or a catalytic combustor to supply bothheat and power as an On-board Auxiliary Power Unit. Here, the APU is asmall IC engine/gas turbine or a combustion device, which can provideboth heat and electricity to a small local area when a large dieselengine or when a large stationary back-up power generator is not inoperation. For example, U.S. Pat. No. 8,397,509 provides a combinationof one catalytic combustor and one steam/gas turbine system to generateheat and electricity.

Depending on the final application, the size/volume of each ATRreformer's reaction zones can be adjusted to provide a reformate withthe appropriate gas composition for the downstream equipments. Forexample, a compact reformer containing only the catalyst in the firstCPO/SR catalyst zone can satisfactorily provide a reformate comprisingH₂, CO and some unconverted fuels for a downstream IC engine/gasturbine; A proper volume combination of CPO/SR, SR and WGS catalysts intheir respective reaction zones can completely convert all thehydrocarbons and/or bio-fuels to produce a reformate comprising themaximum % H₂ and the minimum % CO, and this reformate can be used toregenerate catalysts in the pollution traps. If necessary, this H₂ richreformate can also be used as a small hydrogen station for a distributedfuel cell power generator, and/or as the only fuel source for areformate IC engine/gas turbine.

The fuels mentioned here can be any chemicals selected from one or moreof the following compounds: C₁-C₁₆ hydrocarbons, methane, natural gas,methane hydrate, LPG, C₁-C₈ alcohols, vegetable oils, bio-ethanol,bio-diesel, bio-methane, the industrial waste or vent gas containingvolatile organic compounds (i.e. VOC, mainly organic solvents), and anybio-fuels derived from biomass or from agriculture/industrial/animalwastes. In theory, the ATR reformer's fuel candidates can be any gaseousfuels, liquid fuels or a combination of any fuel mixtures which caneventually be vaporized and catalytically be oxidized over the Pt groupmetal catalysts to produce hydrogen and CO by the autothermal reformingreactions.

Each ATR reformer's reaction zone includes one or more supported Ptgroup metal (pgm) powder (i.e. washcoats) catalysts, and each catalyzedwashcoat contains between 0.01 to 10.0 wt % of total Pt group metalssupported on metal oxide powders. The term “supported Pt group metalpowder catalyst” refers to one or more of Pt, Pd, Rh, Ir, Os, and/or Rumetals which are first impregnated on one or more washcoat powdersselected from the group consisting of Al₂O₃, Ce oxide, Zr oxides, Ce—Zroxide composite, oxide promoters/thermal stabilizers and mixturethereof. Here, the oxide promoters/stabilizers can be one or more oxidesof lanthanum, cerium, praseodymium, Rhenium, Zinc, Tin, calcium,potassium, zirconium, yttrium, barium, strontium, magnesium and mixturethereof. Subsequently, the catalyzed washcoat powder is then coated onthe surface of an high temperature inert carrier to obtain the total Ptgroup metal loading of 0.1 to 2000 g/ft³ of the catalyst volume, and theinert carrier can be a ceramic monolith, metallic monolith, pellet, wiremesh, screen, foam, plate, silicon carbide etc. For the mobiledevices/equipments, monolithic catalysts are preferred. But themonolith, pellet, gauze, wire mesh, screen, foam, plate, static mixer,heat exchanger or other shapes of catalyst's supports can satisfactorybe used for stationary devices/equipments.

To be used as the catalyzed washcoat support, the inert materials mustbe capable of sustaining a temperature between 500° C. to 1100° C.without losing its strength and shape. For example, the inert ceramicsubstrate can be made of alumina, alumina-silica,alumina-silica-titania, mullite, cordierite, zirconia, zirconia-ceria,zirconia spinel, zirconia-mullite or silicon carbide, and the metallicsubstrate can be made of Fecralloy, Kanthal, stainless steel and otherhigh temperature alloys.

To improve the catalyst's durability and the operating life, it isnecessary to optimize and control individually or simultaneously the %fuels, and the H₂O/C, CO₂/C and O₂/C ratios of the feed mixture withinthe specified range (i.e. limits), so that the reactor's catalysttemperature is constantly kept below 1200° C. (preferably <1000° C.).For example, to maintain the catalyst's temperature below 1200° C.without coke formation/accumulation, the H₂O/C ratio of the inlet fuelmixture is preferably kept between 0.05 and 10.0, the O₂/C ratio between0.15 to 0.8, and the CO₂/C ratio between 0.0 and 0.5. However, since agiven hydrocarbon or bio-fuel has its own boiling point, heat ofvaporization, heat of oxidation reactions, tendency to form coke, ratesof catalytic partial oxidation reactions, rates of steam reformingreactions etc, the optimized operating H₂O/C, CO₂/C and O₂/C ratios forthe ATR's inlet fuel mixture will strongly depend on the type of fuels,the catalysts and the reaction temperature and pressure. For example,the bio-methane is composed of approximately 60% methane and 40% CO₂, afuel mixture comprising low O₂/C ratio and high CO₂/C ratio can still beable to keep the catalyst's temperature below 1200° C. because of highheat capacity of CO₂. In other words, the H₂O/C, CO₂/C and O₂/C ratiosfor the ATR's inlet fuel mixture are controlled in a given range so thatthe ATR reformer's maximum reaction temperature is always below 1200° C.

To assist the homogeneous combustion inside an IC engine/gas turbine,the reformate coming out of the ATR reformer can be mixed directly withadditional amount of fuels and fresh air/oxidant as part of theengine/turbine's lean fuel mixture. However, for transient operationswhich are frequently found in mobile, stationary or specialapplications, it is preferred to store the produced reformate in highpressure vessels before admitting it into an engine/turbine. For thisprocess arrangement, the ATR reformer's main function is to produceenough reformate to keep the storage vessels within a pressure rangebetween 1 to 100 atmospheres, and the engine/turbine's hydrogenrequirement can then be withdrawn from the storage vessels. In otherwords, the reformate's storage vessels can act as a buffer, the ATRreformer's operation is directly controlled by the storage vessels'reformate pressure, and it is not necessary for the ATR reformer toresponse directly and spontaneously to any frequently sudden changes inthe engine/turbine's speed/load. Thus, the storage vessels allow thereformers to change from one steady state operating condition to thenext condition smoothly.

In order to have instantaneous control, recording and monitoring of thefuel ratios, the Flex-Fuel H₂ reforming apparatus is required to equipwith necessary sensors, on/off valves, pumps, thermocouples, flowmeters/controllers and either a programmable logic controller (PLC) or amicroprocessor. Furthermore, a personal computer (PC) can be used toprogram and to communicate with the PLC/microprocessor. However, if a PCor a powerful microprocessor is equipped itself with the necessaryinput/output interface modules, it can be used to control and monitordirectly the Flex-Fuel H₂ reforming apparatus.

For mobile applications, the water condensed from the ATR's reformatecan be recycled back to the ATR's inlet feed mixture so that a mobilevehicle does not have to carry a big water tank. Furthermore, to startup the Flex-Fuel H₂ reforming apparatus from room temperature, theengine's recycled exhaust gas can be used to provide heat, O₂ and steamto initiate the oxidation reactions, especially if the ATR's inlet fuelmixture comprises at least one low temperature light-off fuel component.Furthermore, to start or re-start an ATR reformer rapidly, the recycledreformate from the storage vessels and/or the H₂/O₂ gases from the waterelectrolyzer can also be used to initiate and to accelerate theoxidation reactions of other fuels. Since hydrogen-oxygen reaction canproceed over the Pt group metal catalyst at room temperature, theoxidation reaction heat can rapidly increase the catalyst above thelight-off temperatures and, thus, can initiate the oxidation reactionsof other fuels without using any external heating devices. Note that thelight-off temperature is the minimum temperature required to sustain thecatalytic partial oxidation reaction of a given fuel spontaneouslywithout using any external heat sources.

The third reaction zone of this ATR reformer can be used to convertwater and CO to produce H₂ at a slower space velocity by the water gasshift reaction. For this reaction zone, the Pt group metal catalysts,which are supported on oxides such as Al₂O₃, Ce/Zr Oxides, oxide thermalstabilizer/promoters and mixture thereof, are preferred. Here, the oxidethermal stabilizer/promoters can be one or more oxides of lanthanum,cerium, praseodymium, rhenium, calcium, zirconium, yttrium, barium,strontium, magnesium, zinc, potassium, copper, iron, cobalt, nickel,chromium, tin, gold, silver and mixture thereof. But the traditionalCu/Zn oxide and/or Fe/Cr oxide catalysts can also be used in thisreaction zone to increase the % H₂ and decrease the % CO in thereformate gas. However, when a catalyst is not present in this thirdreaction zone, the non-catalytic water gas shift reaction will alsooccur thermodynamically, but with slower reaction rate. Therefore, forthe purpose of regenerating a catalyst without CO emission, the reformershould contain SR and WGS catalysts inside the reaction zones, and acatalytic converter containing Pt group metal catalyst can be used toreduce CO emission after the NO_(x) trap/diesel particulate filter.

As described previously, when hydrogen is added to the inlet fuelmixture, engine can be adjusted to perform lean combustion instead ofthe current near stoichiometric combustion. In addition, by combiningthe lean air/fuel mixture with a turbo charger, an engine can increaseits compression ratio and can improve its thermal efficiency further byperforming lean combustion at a higher pressure. Since the exhaust gasof a lean burn engine comprises mainly N₂, O₂, CO₂ and steam,re-circulating the lean exhaust gas is an effective way to inject steam,O₂, CO₂ and heat into the ATR reformer. Therefore, the recycled exhaustgas can reduce the reformer's heat loss and can continuously keep thereactions inside the ATR's reaction zones without any external heatsources. Also, the steam and CO₂ in the recycled gas can absorb morereaction heats and reduce the reformer's peak temperature below <1200°C.

Portion of the electricity generated by this Flex-Fuel H₂ reformingapparatus can be used to produce HHO gases by the electrolyzer. Howeverif a solar panel and/or a wind power generator are available, they canbe used to supply electricity to perform electrolysis of distilledwater. In this case, the H₂ produced by the electrolyzer is primarilyused to initiate the catalytic partial oxidation reaction of fuelsduring the reformer's start-up period, and it can also be added directlyto the reformate storage vessel as part of the engine's fuel mixture orbe used to regenerate the NO_(x) trap and/or diesel particulate filter;The amount and the flow rate of the H₂/O₂ produced by the electrolyzer,which is controlled by the pressure of the reformate storage vessel andthe control curves, can be used directly as the ATR reformer's onlyoxygen source for the purpose of increasing the % H₂ in the ATRreformate, or it can be added to air or to the engine's recycled exhaustgas to increase the % O₂ content in the ATR reformer's inlet fuelmixture >10%.

As shown in FIG. 1, a system consisting of an on-board Flex-Fuel H₂reforming apparatus and the engine/gas turbine can directly be used byitself as a driving device for general applications, such as automobile,lawn mower, fork lift truck, diesel truck, bus, train, motorcycle etc.If this Flex-Fuel H₂ reforming apparatus and the engine/gas turbinesystem is connected to an electric generator and a battery bank, it cangenerate and store electricity as a stand-alone mobile or stationarypower station. This stand-alone distributed power station can be used topower electric vehicles/equipments, such as automobile, lawn mower,truck, forklift truck, bus, train, motorcycle, portableindustrial/household electrical equipments/devices, electric utilityvehicle, battery charger and backup power. Furthermore, the simplifiedFlex-Fuel H₂ reforming apparatus as shown in FIG. 2, FIG. 3, FIG. 4 andFIG. 5, which are designed to replace FIG. 1 for special simpleapplications, can be used to replace FIG. 1 in the driving device and/orin the distributed power station applications mentioned previously.

For special applications, this Flex-Fuel H₂ reforming apparatus can alsoprovide H₂ or H₂ rich reformate directly to an IC engine/gas turbine asthe only fuel source (i.e. a reformate engine/gas turbine), or it can beused as part of a small portable or mobile distributed hydrogen stationfor supplying H₂ to a fuel cell power generating unit, such as a solidoxide or a proton exchange membrane fuel cell system.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a schematic illustration of a general system comprising aFlex-Fuel H₂ Reforming apparatus, an IC engine/gas turbine and anelectric generator in accordance with an exemplary embodiment of thepresent invention.

FIG. 2 is a schematic illustration of a system comprising an alternatesimplified Flex-Fuel H₂ Reforming apparatus, a lean burn diesel engineand an electric generator in accordance with another exemplaryembodiment of the present invention.

FIG. 3 is a schematic illustration of a system comprising an alternatesimplified Flex-Fuel H₂ Reforming apparatus, a lean burn IC engine andan electric generator in accordance with another exemplary embodiment ofthe present invention.

FIG. 4 is a schematic illustration of a system comprising an alternatesimplified Flex-Fuel H₂ Reforming apparatus, a gas turbine and anelectric generator in accordance with another exemplary embodiment ofthe present invention.

FIG. 5 is a schematic illustration of a system comprising an alternatesimplified Flex-Fuel H₂ Reforming apparatus and a small utility ICengine in accordance with another exemplary embodiment of the presentinvention.

FIG. 6 is a schematic illustration of the shape of catalysts being usedinside the Flex-Fuel H₂ Reforming apparatus in accordance with theexemplary embodiment of the present invention.

FIG. 7 is a schematic illustration of the shape of catalysts being usedinside the Flex-Fuel H₂ Reforming apparatus in accordance with anotherexemplary embodiment of the present invention.

FIGS. 8A and 8B are the schematic illustrations of a large metalliccatalyst being used inside the Flex-Fuel H₂ Reforming apparatus inaccordance with another exemplary embodiment of the present invention.

FIGS. 9A and 9B are the schematic illustrations of a system comprising apersonal computer and a programmable logic controller in accordance withthe exemplary embodiment of the present invention.

FIG. 10 is the illustration of a control curve showing the relationshipbetween the % reformer output capacity as a function of the reformate'spressure in the storage vessels.

DETAILED DESCRIPTION OF THE INVENTION Description of the PreferredEmbodiments

Traditionally, large scale hydrogen is produced industrially byperforming steam reforming (SR) reactions of hydrocarbons over theNi/Al₂O₃ pellet catalyst, and the reformer is commercially operated at alow space velocity (typically at 2,000-8,000/hr) under steady state highpressure conditions. Therefore, to supply H₂ to a mobile equipment or adistributed fuel cell power station, it is required to transport eitherliquid H₂ or high pressure H₂ gas from a long distance central plantand, then, store the H₂ in the local high pressure tanks for theapplications. However, a more convenient approach to supply H₂ for theseapplications is to use a smaller distributed H₂ reformer, which canproduce H₂ locally from various gaseous or liquid fuels. Since a mobilevehicle or a distributed fuel cell power station is typically operatedon the power demand basis, an on-board or a distributed hydrogenreformer must be able to operate satisfactorily under frequent start-up,shutdown and other transient operating conditions.

Using the traditional H₂ production technologies, several smallreformers were designed in the 1970s to convert sulfur containing dieseloil into H₂ for the phosphoric fuel cell application, and thesereformers typically used metal oxide and/or Ni/Al₂O₃ pellet catalysts toperform the catalytic partial oxidation (CPO) and steam reforming (SR)reactions at a low space velocity. But, due to low catalytic activitiesat a slow space velocity, these reformers were generally bulky and theywere not suitable to be used as an on-board reformer. An excellentsummary of these hydrogen production technologies was written by G.Vocks (“Structured Catalysts and Reactors”, edited by Cybulski andMoulijn, Marcel Dekker, Inc. Page 179 (1998)), herein incorporated byreference.

During the development of a new compact reformer in early 1980s, severalmonolithic Pt group metal catalysts were found to be able to produce H₂and CO from a commercial sulfur containing #2 diesel oil at a very highspace velocity. As shown in the DOE report (DE-AC-03-79-ET15383,September 1981), a new ATR reformer, which utilized several monolithicPt/Pd CPO catalysts in the first reaction zone at a space velocity of126,000/hr (18 milliseconds, calculated at 1 atm and 0° C.), can convertmost of the fuels into H₂ and CO and, then, the unconverted fuels can beconverted in the subsequent Pt/Rh SR pellet catalysts in the secondreaction zone at a space velocity of 6,500/hr (i.e. 550 ms).Furthermore, it was later demonstrated that, under proper steady stateoperating conditions, this new improved ATR reformer could alsosuccessfully produce H₂ from diesel oil, gasoline, LPG and JP-4 fuelswithout coke formation.

As shown in Table 1, the total HC conversion of every fuel evaluated inthese experiments was >=99% (dry basis), and the total % (H₂ and CO)produced was >50% under the O₂/C ratio of about 0.38 and H₂O/C ratio ofabout 2.50. Therefore, it can be concluded from these tests that thisimproved compact ATR reformer, which utilizes the monolithic Pt groupmetal catalysts, can successfully be used to produce H₂ from varioushydrocarbon fuels under very high space velocity conditions.

The Pt group metal (pgm) catalysts used in these demonstration tests asdescribed in Table 1 were prepared by impregnating first one or more ofthe Pt, Pd and/or Rh solutions at a given metal concentration into athermally stabilized gama-Al₂O₃ washcoat powder, which had a surfacearea between 50 and 600 m²/g. Here, the thermal stabilizers, which wereused to maintain the surface area of the washcoat powder at hightemperatures, comprise one or more oxides of lanthanum, cerium,praseodymium, rhenium, calcium, potassium, barium, yttrium, zirconium,strontium, magnesium and mixture thereof. Subsequently, the catalyzedwashcoat powder was further coated on the surface of an inert monolithsubstrate, and then dried and calcined. The total combined metal contentof each monolithic Pt group metal catalyst shown in Table 1 wastypically between 0.10 to 2,000 g/ft³.

Though the inert monolith substrate used in Table 1 was a ceramiccordierite which had 200 to 600 straight channels per square inch (CPI),other suitable catalyst carriers can be a ceramic or metallic monolith,foam, plate, gauze, wire mesh, static mixer etc. Here, the ceramicmonolith can be porous materials comprising one or more metal oxidesselected from the group consisting of alumina, alumina-silica,alumina-silica-titania, mullite, cordierite, zirconia, zirconia-spinal,zirconia mullite, silicon carbide etc.; The metallic monolith can be aheat and oxidation resistant alloy such as Fecralloy, Kanthal, stainlesssteel etc.

TABLE 1 Summary of autothermal reforming of hydrocarbons over Pt groupmetal (pgm) catalysts (Hwang et al. AiChe Annual Meeting, Los AngelesCa, Nov. 5, 2000) Hydrocarbon Jet Fuel No. 2 LPG LPG (JP-4) Diesel RunNo. II-41 II-46 II-48 II-32 Catalyst CPO CPO-2B CPO-2B CPO-2B CPO-2B(pgm) (pgm) (pgm) (pgm) S.R. FP-34 FP-34 FP-34 FP-34 (pgm) (pgm) (pgm)(pgm) Condition H₂O/C 2.430 2.480 2.280 2.570 O₂/C 0.398 0.417 0.3810.378 Temperature (C.) Inlet to CPO 749 749 749 749 S.R. TOP 865 896 921942 S.R. MID 717 751 777 809 S.R. END 696 729 758 778 Dry Gas (%) H₂44.35 42.43 39.72 41.11 CO 9.94 10.09 12.49 11.52 CO₂ 12.19 12.17 12.1812.51 N₂ 33.21 35.02 35.23 34.37 CH₄ 0.08 0.04 0.12 0.26 Equivalent H₂2.44 2.36 2.13 2.17 HC Conv. (%) 99.64 99.82 99.50 98.80

To produce hydrogen for fuel cell applications, U.S. Pat. No. 4,522,894had concluded that the rates of partial oxidation reactions of dieseloil over the Pt group metal catalysts are much faster than that of thesteam reforming reactions. In other words, at a the residence time <300milliseconds, the % fuel conversion to make H₂ and CO is primarilycontrolled by the O₂/C ratio of the feed mixture with minor contributionfrom the H₂O/C ratio. However, the related experimental studies as wellas the thermodynamic calculations (DOE #DE-AC-03-79-ET15383 (1981) andDOE #DE-AC-21-79-MC12734 (1981)) had also concluded that the autothermalreforming process, as compared to the catalytic partial oxidationprocess, could widen the operating O₂/C ratios without coke formation,reduce the reactor's peak temperature, extend catalyst durability,minimize the catalyst deactivation and achieve longer reformer life. Inother words, the autothermal reforming process is practically a betterand a preferred process over the catalytic partial oxidation process fora compact durable reformer. For this reason, the patented on-boardreformers developed in the 1970s can be improved for its durability andthe operation life by replacing the CPO reforming process with the ATRreforming process over the more advanced Pt group reforming catalysts,and this new improved Flex-Fuel H₂ Reforming apparatus can be aneffective and efficient on-board H₂ reforming apparatus for a mobilevehicle.

In the late 1990s, a small commercial reformer, which can convert all HCfuels with long durability at a space velocity at about 54,000/hr (i.e.about 67 ms at STP), was developed for a Proton Exchange Membrane fuelcell (PEMFC) electric generator. In this study, a new generation ofadvanced reforming catalysts and a revised compact ATR reformer designwere developed for producing H₂ from natural gas and LPG. Briefly, aseries of layered monolithic CPO/SR catalysts were developed to improvethe steam reforming activities in the ATR reformer's first reactionzone. For these layered catalysts, a thin layer of the SR catalyst wasfirst coated on the inert monolith surface and another layer of the CPOcatalyst was then coated on top of the SR catalyst layer. With theintimate contact between these two catalyst layers, the heat producingCPO layer would generate and quickly provide the reaction heat for theendothermic SR layer without any heat transfer barriers. As shown in theU.S. Pat. Nos. 6,436,363 and 6,849,572, these new advanced catalysts,which were prepared with various multiple layered and/or with variousmetal gradient coating techniques, could achieve the most efficientutilization of the Pt group metals, could further improve the methaneconversion, could reduce the reformer's volume, could reduce thereactor's peak temperature by about 50° C. and most importantly couldprovide a reformer with longer life without coke formation.

Using these advanced reforming catalysts, an improved smaller ATRreformer can be re-designed to produce H₂ from various hydrocarbonsand/or bio-fuels as an on-board reforming unit. For example, a compactand an economic ATR reformer for a mobile equipment can utilize only theCPO/SR catalysts in the first reaction zone without using the SR and WGScatalysts in the second and third reaction zones. This reformer willconvert portion of the fuels into H₂ and CO, and the remainingunconverted fuels and CO can be combusted by a downstream engine/gasturbine. However, for a stationary distributed power generator or for asmall potable hydrogen station, the design and the operating conditionsof an ATR reformer must be adjusted to produce maximum % H₂ and minimum% CO in the reformate. In this case, the ATR reformer should rely on theCPO/SR and SR catalysts in the first two reaction zones to convert all(i.e. 100%) of the fuels into H₂ and CO and, then, rely on thesubsequent WGS catalyst in the third reaction zone to convert CO and H₂Ointo H₂.

For this on-board Flex-Fuel H₂ Reforming apparatus, portion of theelectricity generated by the electric generator as shown in FIG. 1 canbe used by the water electrolyzer to produce pure O₂ and H₂. Theproduced H₂ can be used to heat up catalysts above the light-offtemperatures and, thus, can rapidly initiate the CPO reactions of fuelsduring the start-up period; The produced O₂ can be used to increase theO₂ content in the recycled exhaust gas, can be used alone as an ATR'soxidant or can be used to enrich the combined ATR inlet fuel streammixture to >10% O₂.

U.S. Pat. No. 5,648,582, herein incorporated by reference, described aprocess of using a millisecond (ms) reactor to produce synthesis gassuccessfully from methane over a metal supported catalyst at a veryshort residence time (SV=800,000 to 120,000/hr, or about 3 ms). Here,air and/or pure O₂ were used as oxidants for the CPO reaction, and thecatalysts used in this millisecond reactor system were one or more ofRh, Ni, and Pt catalysts which were coated on the surface of a ceramicfoam substrate, metal gauze or extrudate. Since 1990s, professor Schmidtand his group had successfully produced synthesis gas and olefins overmostly the ceramic Rh foam catalysts at millisecond contact time frommethane, n-hexadecane, n-decane, JP-8, gasoline, diesel oil, ethanol,glycerol, vegetable oil, biodiesel, other volatile and non-volatileliquids etc. Several excellent patents and scientific papers have beenpublished by this group in the last two decades. Overall, their studieshave demonstrated that the volatile hydrocarbons and bio-fuels caneasily be reformed catalytically into H₂, CO and olefins with highyields in an millisecond reactor system, and that the synthesis gas canbe produced from various fuels by either catalytic partial oxidation orautothermal reforming reactions over the Rh containing catalysts, whichwere coated on gauzes, ceramic foams or Al₂O₃ spheres.

In the last two decades, a group at Argonne National Laboratory has alsodone some excellent studies in developing catalysts as well asdeveloping the advanced CPO and autothermal reforming processes. Forexample, U.S. Pat. No. 6,110,861, herein incorporated by reference,described a newly developed two-part catalyst (i.e. 1% Pt/CeGdO pelletcatalyst) which could effectively produce H2 from gasoline/natural gas,water and oxygen fuel mixture with the residence time of 0.1 to 2seconds; U.S. Pat. No. 6,713,040, herein incorporated by reference,described the detailed design and operating procedure for a compactautothermal reformer to produce H2 from fuels for the fuel cellapplication. Overall, the studies by this group had also demonstratedthat H2 could efficiently be produced from iso-Octane, cyclohexane,2-pentene, ethanol, methanol, methane and other fuels over the newlydeveloped Pt containing two-part catalyst by the autothermal reformingprocess.

Since 2000, a lot of excellent patents and scientific papers have beenpublished by various groups worldwide on the catalytic partial oxidationand the autothermal reforming processes, and it is impossible to citeevery study here. However, it is clear from these publications that theCPO and the ATR processes can effectively be used to produce H₂ and/orsynthetic gas catalytically from various volatile hydrocarbons andbio-fuels under very high space velocity conditions (i.e. smallreformer).

For industrial applications, the addition of water/steam to thereformer's inlet fuel mixture will convert a CPO reformer into an ATRreformer, and this ATR reformer which utilizes the advanced reformingcatalysts can effectively be operated under wider range of the O₂/Cratios without coke formation as a stationary H₂ reforming apparatus.Furthermore, to improve over this stationary H₂ reforming apparatus formobile applications, an on-board Flex-Fuel H₂ reforming apparatus, whichprovides several practical devices and the method of operating thesedevices without external heat and electrical sources, can produce H₂from various volatile hydrocarbons and/or bio-fuels for the ICengines/gas turbines.

Though most of the current gasoline IC engines are designed to operatestoichiometrically, the lean burn gasoline and/or diesel truck enginesare becoming more popular in recent years. Since the lean burn ICengines will produce more NO_(x) pollutant as compared to an enginerunning with a stoichiometric air/fuel mixture, a monolithic NO_(x) trapis installed in the exhaust pipe to reduce the NO_(x) emission from alean burn gasoline engine. Similarly, a NO_(x) trap and a dieselparticulate filter are installed in the exhaust line to remove emissionsfrom a lean burn diesel engine.

Typically, a NO_(x) trap and a diesel particulate filter comprise sometrap materials supported on a porous ceramic monolith, and the trapmaterials comprise a small % Pt group metals supported on an Al₂O₃powder and one or more oxides of K, Na, Cs, Ba, La, Sr, Ca, Mg, Zn, Ce,Zr and the mixture thereof. However, each trap material has its ownstorage capacity, and it will not reduce the NO_(x) or dieselparticulate emissions once it is saturated. Therefore, these trapmaterials are required to be regenerated periodically by using anexternal reducing H₂ and/or CO gases, and the Flex-fuel H₂ Reformingapparatus can effectively produce this reducing gas for thisapplication.

The IC engine/gas turbine can be started manually from room temperatureto generate the hot exhaust gas, which is recycled back to heat up theATR reformer and also to drive the electric generator to power up thePLC/ECU and all sensor/controllers. Once the electricity is generated,the whole system can be switched to the automatic operating mode and letthe computer system operate the H₂ reforming apparatus automatically.

The combination of this Flex-Fuel H₂ Reforming apparatus and an ICengine/turbine can be used by itself as a driving device for a mobiledevice/equipment, such as lawn mower, chainsaw, motorcycle, fork lifttruck, automobile, bus, truck and train; The combination of thisFlex-Fuel H₂ Reforming apparatus, an IC engine/turbine, an electricgenerator and a battery bank can be a useful distributed and integratedelectric generating system for an electric car, truck, train,motorcycle, forklift truck, electric utility vehicles, battery charger,backup power generator, and other stationary or mobile electricequipment/devices.

Exemplary Embodiments Described

The on-board Catalytic EGR oxidizer described in U.S. Pat. No. 8,061,120teaches a process of producing H₂ and CO from various hydrocarbons andbio-fuels for the IC engines/gas turbines. To be a successful anddurable reformer without coke formation and without catalystdeactivation and/or melting, the ATR reformer's reaction temperaturesmust be kept constantly <1200° C. (preferably <1000° C.), and the O₂/Cratio of the reformer's inlet fuel mixture must be kept between 0.15 to1.50, the H₂O/C ration between 0.05 to 10.0 and the CO₂/C ratio between0.00 to 0.50. To improve over this Catalytic EGR Oxidizer, an on-boardFlex-Fuel Hydrogen Reforming apparatus as shown in FIG. 1 is designed,and this on-board reforming apparatus can provide practical devices andthe method of operating these devices primarily for mobile vehiclesand/or distributed electrical generators where external power and watersources are limited. Furthermore, using the teachings of the presentinvention, potential simplified on-board Flex-Fuel H₂ Reformingapparatuses and/or other various system configurations are available toone skilled in the art and, as examples, several simplified Flex-Fuel H₂Reforming apparatuses are included here for various specificapplications.

Contrary to a steady state fuel cell reformer, a successfully on-boardreformer must be able to convert fuels into H₂ without coke formationunder rapid transient (i.e. fast acceleration/deceleration), frequentstart-up/shut down, steady state and other unsteady state operatingconditions. Also, it must be able to perform autothermal reformingwithout any external power and water source, and the reformers must beable to be re-started very quickly with the system's own heat andelectricity. Therefore, this Flex-fuel H₂ Reforming apparatus isdesigned to provide several reactant supply paths (loops) for injectingthe necessary reactants into an ATR reformer. Here, the reactant supplypaths include a water loop, a gaseous fuel loop, a liquid fuel loop, awater electrolyzer loop, a recycle water loop, a recycle reformate loop,a recycle exhaust gas loop, and two air supply loops. Briefly, thecontrolled amount of at least one fuel, one oxidant and one water/steamfrom the reactant supply loops are injected into the ATR reformers forconverting the fuels over the Pt group metal catalysts into a reformatecontaining H₂ and CO. The produced reformate will be cooled, thecondensed water will be recycled as one of the ATR reactant and the drygas will be compressed and stored in one or more high pressure storagevessels. As described previously, the pressure of the reformate in thestorage vessel is the primary feedback signal which is used to regulatethe flow rate of each reactant according to the predefined controlcurve. Thus, this pressure signal is used to increase or decrease thetotal amount of the reformate output produced by the ATR reformers, sothat the reformate pressure in the storage tanks can be maintain between30 to 100 atmospheres. In other words, as the pressure of the storedvessels decreases, each reactant's flow rate, while keeping under thesame O₂/C, H₂O/C and CO₂/C ratios, will be proportionally increased andmore reformate with the same gas composition will be produced by thereformer to keep the vessels' pressure within the limits. However, whenthe pressure is closer to 100 atmosphere, one or more ATR reformers willbe operated at a reduced flow capacity, stayed in the idle mode or evenshut down to decrease the total amount of reformate output to thestorage vessels. Due to the fact that the ATR reformers may get shutdown during the operation, it is very important that the reformers canbe re-started very quickly with the system's own heat and electricity.Furthermore, this Flex-Fuel reforming apparatus is typically operated ata temperature between 650° to 1000° C., and it can be used to generatehot water and hot air in a downstream condenser as one part of acombined heat and power generator.

To produce a H₂ rich reformate, the ATR reformer's inlet fuel mixture ispreferred to be controlled at O2/C<0.5. However, this fuel rich mixtureis mostly combustible and potentially explosive, it is thus veryimportant to use proper fuel injectors for each reformer and also tominimize the total amount of fuel mixture injected into a reformer, sothat any damages caused by system malfunctions can safely be reduced.For these reasons, this on-board Flex-Fuel H₂ reforming apparatuscomprises one or more parallel ATR reformers instead of a single largereformer.

The dry reformate is compressed and stored in vessels #10 and #10B at apressure between 30 to 100 atmosphere, and the reformate is then reducedby a regulator #55 a to a lower pressure between 1 to 50 atmosphere inflow manifolds #10A or 10C. Here, the controlled amount of the reformatein manifold #10A (stream #217) and the secondary air (stream #208) aremixed with proper amount of primary fresh air (stream #218) and primaryfuels (stream #201A) to become a lean fuel mixture at a lambda ratiobetween 1.01 to 1.80 for an engine/gas turbine #11 (i.e. Lambdaratio=[actual air/fuel ratio]/[stoichiometric air/fuel ratio]). Portionof the reformate (stream #214) in manifold #10C can be used as areducing gas to regenerate the catalysts in the NO_(x) and dieselparticulate traps. It can also be recycled back as a reactant (stream#215) for rapid start-up of the reformers, and/or can be used to supplyH₂ (stream #216) to an on-board APU #11A. The APU unit will provide heatand electricity in a small remote area when the big diesel engine is notin operation.

The flow meter/controllers shown in FIG. 1 can be metering pumps, massflow meters/controllers or automobiles' electronic fuel injectors. Sinceany one of these flow controllers can regulate precisely the flow rateof a given gaseous and/or liquid reactant according to the predefinedset point, the combination of these flow meters/controllers can thusblend several pure gas and liquid components together by controllingeach reactant flow rate at a given value. Thus, these controllers canprovide the ATR inlet fuel mixture with the specified O₂/C, H₂O/C andCO₂/C ratios according to the set point given to each flow controller bythe control curve, which is stored in the computer control system.Furthermore, by downloading from the computer a new set point to aspecific flow meter/controller, this flow meter/controller can quicklychange the flow rate to a new value with excellent repeatability andreproducibility. In other words, the O₂/C, H₂O/C and CO₂/C ratios andthe total flow rates of the fuel mixture can be maintained and/orchanged to a new value very quickly and precisely by this controlsystem.

For this Flex-Fuel H₂ reforming apparatus system as shown in anexemplary embodiment in FIG. 1, the water reactant loop is consisted oftank #1, metering pump #50, flow valve #51 and flow meter/controller#52; The gaseous fuel reactant loop is consisted of tank #2, pressurereducer #55 a, flow valves #51 and flow meter/controllers #52; Theliquid fuel reactant loop is consisted of tank #3, metering pump #50,valves 51 and flow meter/controllers #52; The water electrolyzer isconsisted of electrolyzer #5, battery #4, gas filters #5A/#5B and flowvalves #51; The water recycle loop is consisted of heat exchanger #7,gas/liquid separator #8, filter #54, metering pump #50 and flow valve#51; The reformate recycle loop is consisted of reformate manifold #10C,compressor #9, flow valve #55 and flow meter/controller #52; The exhaustgas recycle loop is consisted of tank #10E, filter #54, compressor #9,flow valve #55 and flow meter/controller #52; The air loop is consistedof a turbo charger #14, tank #10D, heat exchanger #7, flow valve #55 or#51 and flow meter/controllers #52. Also, another primary air input tothe engine/gas turbine is the flow line #218, which consists of athrottle valve #70 and an air mass flow meter (not shown). Since thison-board Flex-Fuel H₂ reforming apparatus is controlled and operatedautomatically by a computer and/or a programmable logic controller (PLC)#100, the valves and the flow meters/controllers installed in everyreactant loop must be compatible with the computer's input/outputinterface modules. In other words, they must be able to be open, closed,regulated and/or controlled by the computer/PLC system.

The IC engine/gas turbine #11 can be started manually using the currentautomobile's ignition method. In other words, the engine is started withrich combustion using primary air from line #218 and either gaseous orliquid primary fuel in line #201A. Once the engine/gas turbine isstarted, the primary air and fuel flows are both regulated by theposition of the throttle valve #70, which is determined by the driver'sdesire to control the vehicle's speed. Then, the engine/gas turbine willturn the electrical generator #12 to generate electricity and willsupply power to the computer control system #100 and the battery banks#13/#4; The exhaust gas will turn the turbo charger #14 to providesecondary high pressure air for the engine/gas turbine (line #208) andthe ATR reformer (line #210). Afterword, the exhaust gas #211 is splitinto two streams where stream #211A/#212 is recycled back to thereformer to provide heat, O₂ and steam to the reformers, and stream #213will again be split into streams #213A and #213B, so that the NO_(x)and/or diesel particulate pollutants can be removed by traps #17. Notethat a dual trap exhaust pipe system is provided in this system for easeof performing catalyst regeneration. After the traps, the exhaust gaswill pass through a catalyst converter #15 and a muffler #16 beforeventing into atmosphere.

The injector #53 is a specially designed device which can handle theinjections of the combustible fuel, water, oxidant and other reactantssafely. This injector can combine all the reactants together into asingle fuel stream before this fuel mixture is admitted into the firstreaction zone in the ATR reformer #6. By properly controlling eachreactant's flow rate individually and/or simultaneously to obtain thefuel mixture with the specified O₂/C, H₂O/C and CO₂/C ratios, the fuelswill be reformed into H₂ and CO over the Pt group metal catalyst at atemperature <1200° C. and a pressure between 1 to 100 atmosphere. Forperforming safe reforming reactions, the ATR reformer is equipped with athermocouples #56 and a wide band O₂ sensor #53A to fine tune the O₂/Cratio of the fuel mixture before the ATR's first reaction zone. Sincethe reaction temperature is strongly related to the total reaction heatsas well as the O₂/C ratio of the fuel mixture, thermocouples can be usedeffectively to fine tune the O₂/C ratio by adjusting slightly the flowrate of the secondary air flow or primary fuel and H₂ flow. Furthermore,to avoid catalyst deactivation, to have long catalyst life and to avoidcoke formation, it is necessary to install several thermocouples insideand outside the reaction zones to monitor and to provide the feed-backinformation for controlling the O₂/C, H₂O/C and CO₂/C ratios, and alsoto keep the reaction temperature constantly below 1200° C., preferably<1000° C.

The PLC/ECU microprocessor and/or the computer control system #100 iscapable of operating the whole system automatically. For example, whenthe pedal is pressed or released by the driver, the position of thethrottle valve #70 will response to the driver's desire to increase ordecrease the engine speed, and it will increase or decrease theprimarily air flow in stream #218 as measured by the air mass flowmeter, and the primarily fuel flow in stream #201A. If the molar ratioof H₂ flow in line #217/fuel flow in line #201A and the molar ratio ofsecondary air flow in line #208/H₂ flow in line #217 are respectivelycontrolled at a given (constant) value, the position of the throttlevalve and/or the air mass flow sensor will also determine the H₂ flowrate in line #217 and the secondary air flow rate in line #208.Therefore, the position of the throttle valve will simultaneouslydetermine the flow rates in lines #218, #201A, #217 and #208, and thecombination of these flows should provide a lean fuel mixture for theengine/gas turbine at a lambda ratio between 1.01 to 1.80. However, whenengine is required to be operated at high loads, the final fuel mixturemust be adjusted from the lean side to the rich side to produce moreengine power. In this case additional extra fuel from line #201A andextra H₂ from line #217 can be injected into the engine.

Regardless of the engine/gas turbine's speed and load, the controlstrategy is to keep the ratio of H₂ flow in line #217/fuel flow in line#201A at a given value between 0.05 to 0.95, and also keep the ratio ofH₂ flow in line #217/secondary air flow in line #208 at a given value,so that the addition of these H₂ and secondary air flows to the originalfuel mixture (i.e. fuel #201A and air #218) will change it from thestoichiometric (i.e. Lambda=1.00) into a lean burn mixture at a Lambdabetween 1.01 to 1.80 (for gasoline car). In this case, the higher theengine speed, the larger amount of H₂ is required to be injected into anengine/gas turbine and, thus, the faster the pressure is decreased intank #10. As the computer control system detects the decrease in thevessel pressure, it can quickly start up the reformers and/or increasethe reactants' flow rates to produce more reformate, so that thepressure inside vessel #10 can be maintained between 30 to 100atmosphere. Similarly, when the engine speed is decreased, less amountof H₂ is required and the pressure in vessel #10 will be reduced at aslower rate, and the computer control system will then decrease thereactants' flow rates to reduce the amount of total reformate produced.In this case, one or more ATR reformers can either be shut down or beoperating at a reduced capacity when the pressure is closer to the upperlimit.

Contrarily to a steady state fuel cell H₂ generator, an on-board H₂reforming apparatus will mostly be operated under transient operatingconditions, and frequent acceleration and deceleration of a mobilevehicle will create sudden fluctuation in the hydrogen demand. In otherwords, during the operation, the ATR reformers will be shut down, willbe performed at the various flow capacity and will be re-startedfrequently. Therefore, it is critical to be able to re-start thereformers rapidly without external sources of heat and electricity, sothat the reformate pressure in the storage vessel can be maintainedwithin the limits during the sudden acceleration period.

FIG. 2 shows an alternative simplified Flex-Fuel H₂ reforming apparatuswhich is suitable to be combined with a lean burn diesel truck engine.For a long durable system without coke formation, a reformer would liketo be operated under steady state condition and, thus, frequent changesin the flow rates, temperature, O₂/C and H₂O/C ratios should be avoidedor minimized. Unfortunately, a diesel engine will constantly be operatedunder frequent start-up/shutdown, acceleration/deceleration and/or otherunsteady state transient operating conditions. In addition, since thecommercial diesel oil contains some unsaturated high molecular weightcomponents, and since it is very difficult to vaporize these cokeproducing fuel components completely within a very short residence time(i.e. under high space velocity operating condition), a second lighterfuel is used in tank #2 for producing H₂ without coke formation by theon-board reformer, and the commercial diesel oil in tank#3 is still themain fuel for the diesel truck engine. In this design, one of the fuelsselected from the group consist of natural gas, CNG, LPG, gasoline,methanol or bio-ethanol is stored in tank #2, and this fuel isexclusively used by the reformer to produce H₂ and CO reformate as areducing agent for the diesel truck engines. However, for a natural gastruck engine, H₂ can be produced from fuel quickly and it is notnecessary to have dual fuel tanks.

The description of all other devices/equipments in FIG. 2 are the sameas those described in FIG. 1, and the method of operating thissimplified Flex-Fuel H₂ reforming apparatus for the diesel engine issimilar to the method described previously for FIG. 1.

FIG. 3 shows an alternate simplified Flex-Fuel H₂ reforming apparatusfor a lean burn IC engine which uses CNG (compressed natural gas), H₂rich reformate gas, LPG, gasoline, methanol, bio-ethanol or other lightweight hydrocarbons as fuel. Because a lean burn engine will producemore NO_(x) emission, it is necessary to provide H₂ and CO from flowmanifold #10C (stream #214) to regenerate periodically the NO_(x) trap#17.

FIG. 4 shows a simplified Flex-Fuel Reforming apparatus for a gasturbine. Here, the reformate comprising higher % H₂ and the primary fuelare used as the turbine fuel, and the ATR reformer can physically beintegrated into the gas turbine as a single unit. In addition, pure O₂or enriched O₂ gas can be used to replace air for the reforming process,so that the reformate contains higher % H₂ with less % N₂ for the ICengine, gas turbine and solid oxide and/or proton exchange membrane fuelcell devices. In this case, the amount and the flow rate of the H₂/O₂generated by the electrolyzer is directly controlled by the pressure ofthe reformate storage tank and the control curves.

For a small and economic utility engine which uses natural gas, LPG,bio-ethanol or gasoline as fuel, a very simple H₂ generating systemwithout excess accessories is provided as shown in FIG. 5. Here, thefuel from tank #3 is split into two streams. Stream #201 is injectedinto the engine directly, and stream #202 will be reformed into H₂ usingair as oxidant. Also, the recycled exhaust gas is used to provide steam,heat and CO₂ to the ATR reformer, but the amount of the % recycledexhaust gas and the condensed water must be controlled to avoid floodingthe engine with the condensed water.

FIG. 6 and FIG. 7 describe the shape of the catalysts used in thereformer. For example, the ATR reformer comprising only the CPO/SRcatalysts in the first reaction zone will typically have catalyst shapeas shown in FIG. 6, and an reformer comprising catalysts in all threeCPO/SR, SR and WGS reaction zones will have catalyst shape as shown inFIG. 7. Also shown in these figures, a back-up flame igniter E isinstalled before the first catalyst sample for the purpose of initiatingthe CPO reactions manually.

For a large round metallic monolith catalyst, it is very difficult tomeasure the fresh and the aged catalytic activities in the laboratory.Therefore, one single large metallic monolith catalyst is designed toconsist a smaller catalyst core at the center, and a large annularcatalyst core on the outside, as shown in FIG. 8A and FIG. 8B. Thesmaller catalyst core in the center is designed to be able to removefrom the whole unit without destroying the outside annular core, so thatits catalytic activity can be evaluated by a laboratory testing unit.This catalyst design is especially useful to determine if an aged or aregenerated catalyst is still effective in reducing the emissions, andalso to measure the rate of the catalytic deactivation as a function oftime on stream. If necessary, the smaller catalyst core can either berestored back into the same location or be replaced by an identicalfresh one after laboratory activity evaluation.

FIG. 9B shows the brain of the whole control system and it isrepresented as FIG. 9A in FIGS. 1 through 5. Here, a programmable LogicController (PLC, D2-260CPU unit from www.automationdirect.com) isconnected and communicated to a HP PC computer through a RS-232 or anEthernet cable, and this CPU module can also communicated with severalinput/output interface modules. Here, the main computer control softwareof the whole system is installed in the PC, and the PC will download agroup of pre-calibrated set points to the PLC, which in term willtransmit the control signal to the proper I/O module and carry out theactual control actions by the controllers. In other words, Once theinterface modules receive the control signals, they can control andmonitor pumps, flow meters/controllers, valves, thermocouples, O₂ sensorand other devices in the system. Similarly, each device's status and thesensors' signal can transmit to the PLC and the PC via the reversesignal paths.

FIG. 10 demonstrates one of the control curves which shows the total %reformate output from the ATR reformers as a function of the pressure invessels #10 and #10B. Here, each point in the curve represents acomplete group of pre-calibrated set points for all flowmeters/controllers at the same specific O₂/C, H₂O/C and CO₂/C ratios,and at a given total reformate output from the reformers. Typically, asa given group of set points is downloaded from the PC to the PLC, thePLC will transmit the pre-calibrated set point to each flowmeter/controller in the system and adjust each reactant's flow rateaccordingly. Therefore, by blending all the individual reactant flowtogether, the O₂/C, H₂O/C and CO₂/C ratios of the reformers' inlet fuelmixture can be controlled at a specific value and, thus, can produce thereformate with the same gas composition. In other words, every point inthis control curve can actually provide the fuel mixture and thereformate with the same composition, but at a different total flowrates. Similarly, the pre-calibrated control curves for other fuelmixtures with different O₂/C, H₂O/C and CO₂/C ratios and various flowrates can also be provided. Therefore, the same reformer has theflexibility of being used to produce H₂ and CO reformate from variousfuels and/or bio-fuels.

For a smaller system, the functions of the PC and the PLC as shown inFIG. 9B can be replaced by a powerful microprocessor, or by a small PCwith the necessary I/O modules installed. Therefore, the automaticoperation of this system can be done easily by a single alternativepowerful control device.

Example

Several fully automatic laboratory reactor systems, which had adoptedthe similar control strategy as shown in FIG. 9B, had been assembled inthe past. The reactor systems were used either to produce hydrogen fromhydrocarbons and/or bio-fuels, or to evaluate catalytic activities ofthe laboratory experimental catalysts. These systems were very easy tooperate and very reliable for performing daily routine experiments forseveral years.

Example 1

A larger laboratory reactor system which had more I/O modules than theone shown in FIG. 9B was used to study the catalytic autothermalreforming of bio-ethanol for hydrogen production. Here, a Simatic S7-400PLC, all interface modules and the step-7 communication software werepurchased from Siemens, and were installed and assembled together with alaptop computer as the main control computer.

A custom master control program stored in the main laptop computer waswritten in visual Basic to run the whole reactor system automatically.To operate the laboratory reactor system, the operator pushed thestart-up button, turned on the external power supply relays andinitiated the control program to start the test. According to theprocedures written in the master control program, the PC would downloadthe pre-defined set points simultaneously to the mass flow meters,metering pumps and furnaces. It would then turn on the solenoid valvesaccording the pre-determined sequence to blend the fuel mixture from thepure gas/liquid supply tanks and provided a given fuel mixture with thespecified O₂/C and H₂O/C ratios to the ATR reformer. Subsequently, thecontrol program could start heating the furnaces, and could control andmonitor/record the reactor temperatures and gas compositions. In otherwords, the control system, just like a technician, could perform thecomplete test procedures and record the test results automaticallyaccording to the procedures written in the master control software.

TABLE 2 Autothermal Reforming of bio-Ethanol to Produce H₂ (Hwang, 2006NATPA Annual Conference, Newark, California, Jul. 29, 2006). Product GasVolume %, (dry) H₂ 37.53 O₂ 0.00 N₂ 39.26 CH₄ 0.00 CO 7.52 CO₂ 16.58C₂H₅OH 0.00

An Agilent's Micro GC (model: refinery gas analyzer) was used to analyzethe inlet reactant and the product gas compositions; The catalyst usedwas a ceramic monolithic catalyst (400 CPI) containing 80 g/ft³ totalmetals (Pt/Pd/Rh/CeO₂—Al₂O₃—ZrO₂, 2/1/1 metal ratio), and the ethanol,water and air feed rates were 10.54, 22.50 and 23.57 moles/hrrespectively (i.e. H₂O/C=1.07; O₂/C=2.34). The test results at the inlettemperature of 262° C. are shown in Table 2. Note that the complete 100%ethanol conversation was observed, and that the reactor was reliable fordaily operation with excellent repeatability and test reproducibility.

Example 2

As shown in FIG. 9B, a DL-260 CPU PLC with digital input, digitaloutput, analog input, analog output, ethernet communication module andthermocouple interface modules were purchased from www.AutomationDirect.com; In this simple and cheaper control system, the valves #51are connected to the digital output module; The mass flow meters (Tylanmass flow meters from www.ebay.com) and one water metering pump (modelQV-#RHOCKC from Fluid Metering Inc.) are connected to the analog outputand also to the analog input modules, and several type K thermocouplesare connected to the thermocouple module.

A small Acer ASPIRE ONE laptop computer running Window XP is used as amaster computer. A master control software which is written in visualBasic is used to download flow controllers' set points, to open/closevalves, to monitor/control reactor temperatures, to monitor/record thestatus of each device, to carry out the experimental sequences and themethod of operating this Flex-Fuel H₂ reforming apparatus automatically.

This PLC control system is configured by Directsoft software and it cancommunicate with the ACER PC via KEPDirect communication software (bothsoftware were purchased from Automationdirect.com). The KEPDirectcommunication software can actually operate the whole control systemmanually.

The following is a listing of selected figure elements as alreadymentioned in the specification above:

-   #1 water reactant loop tank-   #2 gaseous fuel reactant loop tank-   #3 liquid fuel reactant loop tank-   #4 battery for water electrolyzer-   #5 water electrolyzer-   #5A gas filter-   #5B gas filter-   #6 ATR reformer-   #7 respective heat exchangers of water recycle loop and air loop-   #8 gas/liquid separator of water recycle loop-   #9 compressor of reformate recycle loop and exhaust gas recycle loop-   #10 dry reformate storage vessel-   #10B dry reformate storage vessel-   #10A flow manifold-   #10C reformate manifold of reformate recycle loop-   #10E tank of exhaust gas recycle loop-   #10D tank of air loop-   #11 IC engine/gas turbine-   #12 electrical generator-   #100 programmable logic controller (PLC)

I claim:
 1. An on-board Flex-Fuel H₂ Reforming device, comprising: (a)one or more parallel autothermal reformers (ATRs) to produce a reformatecomprising H₂ and CO from a fuel, said fuel comprising a hydrocarbon, abio-fuel, or combinations thereof; (b) at least one of a supportedcatalyst or an unsupported catalyst disposed in the ATRs, the at leastone supported or unsupported catalyst including one or more of Pt, Pd,Rh, Ir, Os, and Ru; (c) an ATR reformer fuel mixture inlet in fluidcommunication with the one or more parallel ATRs to provide reactantsthereto, said inlet comprising at least one of a liquid fuel loop, a gasfuel loop, a water supply loop, an air supply loop, a water electrolyzerloop, an exhaust gas recycle (EGR) loop, a water recycle loop and areformate recycle loop, the reactants including i) water and/or steam,ii) an oxidant and iii) said fuel; (d) an automatic control systemoperably connected with the fuel mixture inlet and the one or moreparallel ATRs, said automatic control system configured to maintain aselected O₂/C ratio, a selected H₂O/C ratio, a selected CO₂/C ratio anda maximum ATR reaction temperature below 1200° C., the automatic controlsystem including a flow control curve to regulate the reformate output,wherein a single point on the flow control curve provides a group ofpre-calibrated and stored set points for a respective flow controllerassociated with each reactant, (e) a reformate vessel to store thereformate produced in the one or more parallel ATRs; and (f) a dryreformate storage vessel in fluid communication with the reformatevessel to store a dried form of the reformate, and wherein the flowcontrol curve regulates a total reformate output as a function of thepressure in the dry reformate storage vessel.
 2. The device of claim 1,comprising at least one of an internal combustion (IC) engine, a gasturbine and a fuel cell device in communication with said dry reformatestorage vessel to receive the dry reformate for combustion the at leastone of an (IC) engine, gas turbine, and fuel cell device.
 3. The deviceof claim 2, wherein the gas turbine is configured to drive at least oneof an electric generator, an automobile, a lawn mower, a fork lifttruck, a diesel truck, a bus, a train and a motorcycle.
 4. The device ofclaim 2, wherein the IC engine is configured to drive at least one of anelectric generator, an automobile, a lawn mower, a fork lift truck, adiesel truck, a bus, a train and a motorcycle.
 5. The device of claim 1,comprising at least one of a standalone distributed mobile and astationary power station configured to receive electricity generated bythe at least one of an (IC) engine, gas turbine, and fuel cell device.6. The device of claim 1, wherein the automatic control system includesone or more of i) a flow control curve to regulate the flow rate of eachreactant, and ii) a composition control curve to regulate a dryreformate composition of the dry reformate.
 7. The device of claim 1,wherein an inlet fuel mixture to a selected ATR is provided at O₂/C,H₂O/C and CO₂/C ratios according to said set points.
 8. The on-boardFlex-Fuel H₂ Reforming device of claim 1, comprising at least one of alean burn engine or a gas turbine as a driving device for at least oneof: an electric generator, an automobile, a lawn mower, a fork lifttruck, a diesel truck, a bus, a train or a motorcycle in communicationwith said dry reformate storage vessel to receive the dry reformate forcombustion therein.
 9. The on-board Flex-Fuel H₂ Reforming device ofclaim 1, comprising at least one of a lean burn engine or a gas turbineas the driving device for an electric generator configured as anon-board electric charger for an electric vehicle, the lean burn engineor a gas turbine in communication with said dry reformate storage vesselto receive the dry reformate therefrom for combustion therein.
 10. Theon-board Flex-Fuel H₂ Reforming device of claim 1, comprising at leastone of an automobile, a lawn mower, a truck, a forklift truck, a bus, atrain, a motorcycle, a portable industrial electrical equipment, aportable industrial electrical device, a portable household electricalequipment, a portable household electrical device, an electric utilityvehicle, a battery charger or a backup power source in communicationwith said dry reformate storage vessel to receive the dry reformatetherefrom for combustion therein.
 11. The on-board Flex-Fuel H₂Reforming device of claim 1, comprising at least one of a mobileelectric vehicle and an electric device equipped with: at least one of asolid oxide membrane fuel cell stack and a proton exchange membrane fuelcell stack in communication with said dry reformate storage vessel toreceive the dry reformate therefrom for combustion therein.
 12. Theon-board Flex-Fuel H₂ Reforming device of claim 1, wherein the at leastone supported or unsupported catalyst includes a high temperature inertcarrier with a catalyzed washcoat powder and a total Pt group metalloading of 0.1 to 2000 g/ft3 of a catalyst volume.
 13. A method of usingan on-board Flex-Fuel H₂ Reforming device, comprising: providing theon-board Flex-Fuel H₂ Reforming device of claim 1; providing an inletfuel mixture to the fuel mixture inlet, said inlet fuel mixturecomprising said fuel, H₂O, and O₂; reacting said inlet fuel mixture withat least one of said catalysts inside the one or more parallel ATRs toproduce a reformate containing H₂ and CO from said fuel, andsimultaneously controlling at least one of an O₂/C ratio, a H₂O/C ratioand a CO₂/C ratio of the inlet fuel mixture; maintaining a maximum ATRreaction temperature below 1200° C.; storing a dry reformate producedfrom the one or more parallel ATRs in the dry reformate storage vesselat a storage pressure between 1 to 100 atmospheres; using the flowcontrol curve to regulate the reformate output; supplying said dryreformate to at least one of an internal combustion engine (IC), a gasturbine or a fuel cell device; and combusting said dry reformate in theat least one of an internal combustion engine (IC), gas turbine or fuelcell device.
 14. The method of claim 13, comprising using the flowcontrol curve to regulate at least one of a reactant flow rate, a dryreformate composition of the dry reformate, and a total reformer flowoutput by the storage pressure in said dry reformate storage vessel. 15.The method of claim 13, comprising: maintaining a first catalyticpartial oxidation/steam reforming CPO/SR) reaction zone in the one ormore parallel ATRs while maintaining at selected respective values theO₂/C ratio, the H₂O/C ratio and the CO₂/C ratio of the inlet fuelmixture to create a reformate mixture; reacting said inlet fuel mixtureover at least one of the supported and unsupported catalysts for lessthan a 300 millisecond residence time as calculated at standardtemperature and pressure (STP) in the first CPO/SR reaction zone;reacting the fuel and the reformate mixture over at least one of thesupported and unsupported catalysts for less than 5 seconds in a secondsteam reforming (SR) reaction zone of the one or more parallel ATRs;producing a reformate stream at a reformate temperature between150-1200° C. and at a reformate storage pressure between 1 to 100atmospheres, wherein said reformate stream comprises at least one of areformate H₂, a reformate CO, a reformate CO₂, a reformate N₂, areformate O₂ and an unconverted portion of the fuel; feeding theproduced reformate stream into a water gas shift (WGS) reaction zone ofthe one or more parallel ATRs for less than 100 seconds; and convertinga portion of the water in the inlet fuel mixture and a CO in the inletfuel mixture into hydrogen by utilizing at least one of the supported orunsupported catalysts and a Cu/Zn oxide catalyst at a temperaturebetween 50-500° C.
 16. The method of claim 13, comprising producing a H₂reformate and a CO reformate as a reducing agent and regenerating thesupported or unsupported catalyst in the one or more ATRs using the H₂and CO reformate as a reducing agent.
 17. The method of claim 13,comprising: maintaining a vessel pressure of the reformate in the dryreformate storage vessel between 30 to 100 atmospheres, therebypermitting said vessel pressure to start up and shut down the on-boardFlex-Fuel H₂ Reforming device; and adjusting the flow output of the oneor more parallel ATRs according to the flow control curve.
 18. Themethod of claim 14, further comprising regulating the reformate pressureof the dry reformate storage vessel to regulate the reactant flow rateaccording to the flow control curve, and is therefore used to increaseor decrease a total amount of a reformate output by the one or moreparallel ATRs with a specified dry reformate composition according tosaid O₂/C, H2O/C and CO₂/C ratios of said inlet fuel mixture.
 19. Themethod of claim 16, wherein the on-board Flex-Fuel H₂ Reforming deviceincludes at least one of an internal combustion (IC) engine, a gasturbine and a fuel cell device in communication with said dry reformatestorage vessel to receive the dry reformate for combustion the at leastone of an (IC) engine, gas turbine, and fuel cell device and includes anNOx trap and a catalytic converter in gaseous communication with anexhaust of the at least one of an (IC) engine, gas turbine, and fuelcell device, the method including: reducing the supported and/orunsupported catalysts; regenerating a catalyst in the catalyticconverter; and removing particulates in the NOx trap using the reformatein the dry reformate storage vessel as a reducing gas.
 20. The method ofclaim 13, comprising supplying at least one of a H₂ and a H₂ richreformate to at least one of an IC engine, a gas turbine, a fuel celldevice, and a catalytic combustor to supply both heat and power as anon-board Auxiliary Power Unit.
 21. The method of claim 13, wherein saidfuel is selected from one or more of a C1-C16 hydrocarbon, a methane, anatural gas, a methane hydrate, a LPG, a C1-C8 alcohol, a vegetable oil,a bio-ethanol, a bio-diesel, a bio-methane, an industrial waste, a ventgas containing a volatile organic compound, an agriculture biomass wastebio-fuel, an industrial biomass waste bio-fuel, and an animal biomasswaste.
 22. The method of claim 14, comprising: controlling the dryreformate storage vessel pressure using the flow control curve; andchanging at least one of an amount of H₂ production, an amount O₂production, a H₂ flow rate and an O₂ flow rate.
 23. The method of claim14, wherein the at least one flow control curve provides a totalpercentage reformate output capacity from the one or more parallel ATRsas a function of said reformate pressure in the dry reformate storagevessel.